Process of preparing amino-sulphonic acids substituted in the amino group by acyl radicals of fatty acids



Patented Mar. 9, 1943 onoor BY non. y ACIDS The present invention relates to a process of ::preparing amino-sulphonic acids substitutedin 1. sulphonlc acids in the amino-group of which one ritoors's or PREPARING AMINO-SULPHON- 1o. ACIDS suns'rrruren IN: THE AMINO 2 3 5 'UNITED STATES PATEN OFFICE RADICALS OF FATTY un-ichlYamashita, Kamikyoku, Kyotonand Tokuzo Yoshizakl, Asahiku, Osaka, Japan, a signers, by mesne assignments t'o General An- 1 Y i lline & Fil'mflorporatlon, New .York, N. Y.j,a'

corporation'of Delaware V ,5. :iNo Drawing. I Application lunerzli, 1 939," S eria:l No.280,058. In JapanJune 10,1937 I J 6 Claims. (or 360-401) acids, basesandsalts and very, good properties as washing, wetting, emulsifying and softening I agents. With regard to their washing power they hydrogen atom is substituted by the acyl'radical of a fatty acid. The process consists in causing H reaction products, obtained by the action of aldehydes or ketones on sulphites, to condense with ffatty acid amides. g

, The fatt acid-amidesareeasily accessible by dehydrating ammoniumisalts of fatty acids by a'-he'at treatment or by dehydrating ;the fatty acids by a heat treatinent while passing "ammonia ;gas through the fatty acids. The aldehyde bisulphit es or ketone bisulphite's. are. easily ob- A i industrial sodium .formaldehyde bisulphite are tained in the usual manner knownas determinatlon methodor purifying method. 1

In ,order to condense both products it sufiices tomixthem simply and to dehydratethem under "atmospheric or reduced pressure by heating. No

complicatedapparatus, special vessels and. troucorrespondif the. conditions are the same, with all the products now in commerce.

As fatty acids which may beused in the process of the present invention there maybe used above all the fatty acids having at least 6 carbon atoms,

furthermore, there may be mentioned vegetable and animal fats, oils, waxes and resins or fatty phatlc acids. 3

acids contained in mineral oils or aromatic alii invention but they are not intended to limit it I thereto; the parts are by weight;

(1) Equal parts of oleic acid amide and of heated together to 155 C., whilestirring. After 1 /2 hours reacti on set in with aslight rise of In. some cases it. maybe advantageous to work in the presence of an organic solvent ofhlgh boiling point,j for instance xylene, dichlorobenzenefior pyridine.

When using one of th two first mentioned substances it is possible to reamideused as parent material is soluble in wate or has acertain afllnity forthe water.

Thetemperature of reactionvaries within wide limits according to the parent materials used.

amides of fatty acids of high molecular. weight 7 are. used as parent material the most favorable. temperature of reaction lies between C. and

C. In general, the reactions maybe carried out without application of pressure.

Only in ymove the; water of reaction, which has been"- miormed, very easily from; the mixture by means of azeotropic. distillation.

jsaidreactions. may also be performed in an aque- ,ous medium especially in case the 'carboxylic acid In many cases the the temperature. The; thinly-liquid mass, which at first froths feebly, becomes viscous in the course of a further 3 hours but canstill be stirred.

'Atest portion thereof dissolves even in cold water to a slightly turbid solution and has a very good foaming power. By stirring for further 9 [hours at C. a yellowish powderis obtained which dissolves in water to an entirely clear and colorless solution. The product which has been crystallized from dilute methanol is found by analysis to have the formula CrzI-IaaCQNI-LCHzSOgNa Instead of the oleic acid amide the lauric amide may be used withthesame success.

while stirring, the xylene which distils being replaced by the same quantity of xylene. In order to facilitate the distillation of the xylene and the water of reaction a slightly reduced pressure may be; used. Afterstirring for several hours,

the xylene is blown off by means of steam. The

productdissolvesin warm water to a clear solueon. while frothing strongly. ,The solution remains clear even on addition of dilute hydrochloric acid. V i w (3) 20 parts of commercial lauric acid amide and 45 parts of commercial acetaldehyde sodium bisulphite are heated, while stirring, for 4 hours at 155 .C. After recrystallization, there is obtained a white powder which is soluble in water to a clear solution and foams very strongly even in an acid solution. For many commercial pur-" acid.

(2) 28 parts of oleic acid amide are dissolved. in 30 parts of xylene. 32 parts of formaldehyde poses it is, however, not necessary to recrystalize the product, since it may also be used-in the crude form.

(4) In the same manner as indicated invEX- ample 3, a powder having the same good properties is obtained from 84' parts of commercial oleic acid amide and 138-parts of commercial acetone sodium bisulphite by heating the components for 3% hours at 155 C. and for 6%,hours at 180 C.

In the manufacture.of soap fatty acids from paraifln there is also-formed an important proportion of carboxylic acids containing 5 to 11.

carbon atoms in the molecule whichare assuitable for the present process as the soap fatty acids. An acid containing '7 carbon atoms is, by means of ammonia, transformed into the corresponding acid amide melting at 83 C. to 89 C. A mixture of 39 parts of 'this'acid amide and 84 'parts of commercial formaldehyde sodium bisulphite is maintained, for 3'1101115, at attemperature of 155 C. Stirring isv continued for some time and there is thus obtained, without any'further"puriflcation, 'a product which dissolves'in water to a clear solutionand gives rise to the formation of a strong foam.

. (6) 280 parts of oleic. acid. amide obtained from technical oleic acid are mixed with 220 are'mixed with 150 parts of coconut oil acid amide. By carrying out the reaction at 160 C.

in the same manner as described in Example 6 a white product is obtained which is dissolved in the quantity of sulphuric acid necessary to decompose the formaldehyde-bisulphite in excess and then again neutralized by means of caustic alkali. A white paste-like washing and wetting agent is obtained which is very stable towards hard water and acids.

(10) 1 part of abietic acid amide is intimately triturated together with 1 part of formaldehyde- I sodium-bisulphite and the mixture is heated in an oil bath while stirring, for 3% hours at 150 C. to 160 C. and forfurther 4 hours at 180 C. to 185 C. After entire removal of unaltered abietic acid amide by means of acetone there are ob-.

tained 1.4 parts of a reaction product which dissolves in water to a clear, foaming solution. The

sodium abietinoylaminomethane-sulphonate is a light yellow powder,

' 1. The process of producing a compound having'the following formula:

parts of formaldehyde-bisulphite paste of '90 per cent strength, then melted by heating and stirred in order to evaporateweiter contained therein.

- The temperature is raised to 120 C. to 170 VC.

and then theproduct'is allowed to stand at this temperature untila test portion taken from it dissolves in water to a clear solution. A white condensation product, forming a powder, is ob tained whichpossesses a high wetting and wash- 7 ing' efl'ect and shows stronglstability towards acids, bases and salts.

. (7)- To amixture consisting of 90 parts of oleicacid. amide and 10 parts of, oleic acid 30 4 parts of a fonnaldehyde-bisulphit'e paste of 90 per cent. strength are added and the whole is heated for 5 to-6 hours-at .l20 C. to 160? C. in

order: to remove water contained therein. A

product is obtained, forminga powder which has the same good properties as the product obtained according to'the process of Example 6. It is distinguished from the product of Example 6 by u a higher solubility in cold water and much better stability towardsacids and hard water.

(8) 100 parts of sperm oil acid amide are mixed with 250. parts of a formaldehyde-bisulphite paste of. 90 per cent. strength and the whole is then worked up'as described inExample 6. A prodnot is obtained; which possesses-a very good washing powder and is distinguished especially as emulsifying agent.

(9) 510 parts of :a solution of percent strength of neutral sodium sulphite are mixed with 175 parts of aqueous formalin of 35 per cent.

U f curiaaconncnasom and its sodium-salt, which process comprises condensing a mixture of. oleic acid and a member "selected from the group consisting of sodium formaldehyde bisulphite and formaldehyde bisulphite byheating the mixture to a temperature Which evaporates the'water formed by the conden'sation of the reagents and continuing the heating-until the condensation is complete, the

' reaction being carried out'at pressures not exceeding atmospheric and in the absence of diluents and catalysts.

2. The process of manufacturing aminosulphonic acids substituted in the amino group by an acyl radical of a 'fattyacid containing at least six carbon atoms, which comprisescondensing an amide of afatty acid containing at least six carbon atoms with the reaction products resulting from bisulphites and a member ofthe group consisting of aldehydes and'ketonesythe condensation being carried out by heating to a tempera- "ture which causes evaporation of the water formed during the condensation and at a pressure not exceeding atmospheric, said process being carried out in the absence of diluents and catalysts.

3. The process as in claim 2 in which the amide is condensed with a formaldehyde bisulphite compound. H

4. A process as in claim 1 in which the temperature at which the condensation is effected is 155C.

. 5. A process as in claim 2 in which lauric acid amide is condensed with acetaldehyde sodium strength. The alkali obtained as a by-product; is

neutralized by means of sulphuric acid, water is evaporated and 200parts of. the'formaldehydebisulphite paste of per cent. strength obtained 5 bisulphite. 1

6. A process as in claim 2 in which oleic acid amide is condensed with acetone sodium bisulphite. r

. SHUN-ICHI YAMASHITA.

TOKUZO YOSHIZAKI. 

